Abstract
Magnesium batteries have long been pursued as potentially low-cost, high-energy and safe alternatives to Li-ion batteries. However, Mg2+ interacts strongly with electrolyte solutions and cathode materials, leading to sluggish ion dissociation and diffusion, and consequently low power output. Here we report a heterogeneous enolization chemistry involving carbonyl reduction (C=O↔C–O−), which bypasses the dissociation and diffusion difficulties, enabling fast and reversible redox processes. This kinetically favoured cathode is coupled with a tailored, weakly coordinating boron cluster-based electrolyte that allows for dendrite-free Mg plating/stripping at a current density of 20 mA cm−2. The combination affords a Mg battery that delivers a specific power of up to 30.4 kW kg−1, nearly two orders of magnitude higher than that of state-of-the-art Mg batteries. The cathode and electrolyte chemistries elucidated here propel the development of magnesium batteries and would accelerate the adoption of this low-cost and safe battery technology.
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The authors declare that the data supporting the findings of this study are available within the article and its Supplementary Information files.
References
Liang, Y., Dong, H., Aurbach, D. & Yao, Y. Current status and future directions of multivalent metal-ion batteries. Nat. Energy 5, 646–656 (2020).
Yoo, H. D. et al. Mg rechargeable batteries: an on-going challenge. Energy Environ. Sci. 6, 2265–2279 (2013).
Choi, J. W. & Aurbach, D. Promise and reality of post-lithium-ion batteries with high energy densities. Nat. Rev. Mater. 1, 16013 (2016).
Suo, L. et al. ‘Water-in-salt’ electrolyte enables high-voltage aqueous lithium-ion chemistries. Science 350, 938–943 (2015).
Attias, R., Salama, M., Hirsch, B., Goffer, Y. & Aurbach, D. Anode-electrolyte interfaces in secondary magnesium batteries. Joule 3, 27–52 (2019).
Mohtadi, R. & Mizuno, F. Magnesium batteries: current state of the art, issues and future perspectives. Beilstein J. Nanotechnol. 5, 1291–1311 (2014).
Wan, L. F., Perdue, B. R., Apblett, C. A. & Prendergast, D. Mg desolvation and intercalation mechanism at the Mo6S8 chevrel phase surface. Chem. Mater. 27, 5932–5940 (2015).
Canepa, P. et al. Odyssey of multivalent cathode materials: open questions and future challenges. Chem. Rev. 117, 4287–4341 (2017).
Sun, X. et al. A high capacity thiospinel cathode for Mg batteries. Energy Environ. Sci. 9, 2273–2277 (2016).
Dong, H. et al. Directing Mg-storage chemistry in organic polymers toward high-energy Mg batteries. Joule 3, 782–793 (2019).
Li, Z. et al. Fast kinetics of multivalent intercalation chemistry enabled by solvated magnesium-ions into self-established metallic layered materials. Nat. Commun. 9, 5115 (2018).
Yoo, H. D. et al. Fast kinetics of magnesium monochloride cations in interlayer-expanded titanium disulfide for magnesium rechargeable batteries. Nat. Commun. 8, 339 (2017).
Fan, X. et al. A universal organic cathode for ultrafast lithium and multivalent metal batteries. Angew. Chem. Int. Ed. Engl. 57, 7146–7150 (2018).
Kim, H. et al. Sodium intercalation chemistry in graphite. Energy Environ. Sci. 8, 2963–2969 (2015).
Aurbach, D. et al. Prototype systems for rechargeable magnesium batteries. Nature 407, 724–727 (2000).
Tutusaus, O. et al. An efficient halogen-free electrolyte for use in rechargeable magnesium batteries. Angew. Chem. Int. Ed. Engl. 54, 7900–7904 (2015).
Zhao-Karger, Z., Gil Bardaji, M. E., Fuhr, O. & Fichtner, M. A new class of non-corrosive, highly efficient electrolytes for rechargeable magnesium batteries. J. Mater. Chem. A 5, 10815–10820 (2017).
Shao, Y. et al. Nanocomposite polymer electrolyte for rechargeable magnesium batteries. Nano Energy 12, 750–759 (2015).
Rajput, N. N., Seguin, T. J., Wood, B. M., Qu, X. & Persson, K. A. Elucidating solvation structures for rational design of multivalent electrolytes—a review. Top. Curr. Chem. 376, 19 (2018).
Yamin, H. Lithium sulfur battery. J. Electrochem. Soc. 135, 1045 (1988).
Merritt, M. V. & Sawyer, D. T. Electrochemical reduction of elemental sulfur in aprotic solvents. Formation of a stable S8− species. Inorg. Chem. 9, 211–215 (1970).
Du, A. et al. An efficient organic magnesium borate-based electrolyte with non-nucleophilic characteristics for magnesium–sulfur battery. Energy Environ. Sci. 10, 2616–2625 (2017).
Huang, X. et al. Cyclic voltammetry in lithium–sulfur batteries—challenges and opportunities. Energy Technol. 7, 1801001 (2019).
Suga, T., Pu, Y.-J., Oyaizu, K. & Nishide, H. Electron-transfer kinetics of nitroxide radicals as an electrode-active material. Bull. Chem. Soc. Jpn. 77, 2203–2204 (2004).
Martínez-Cifuentes, M., Salazar, R., Ramírez-Rodríguez, O., Weiss-López, B. & Araya-Maturana, R. Experimental and theoretical reduction potentials of some biologically active ortho-carbonyl para-quinones. Molecules 22, 577 (2017).
Rüssel, C. & Janicke, W. Heterogeneous electron exchange of quinones in aprotic solvents: part III. The second reduction step of p-benzoquinone and its dependence on the supporting electrolyte. J. Electroanal. Chem. Interf. Electrochem. 199, 139–151 (1986).
Lehmann, M. W. & Evans, D. H. Anomalous behavior in the two-step reduction of quinones in acetonitrile. J. Electroanal. Chem. 500, 12–20 (2001).
Nikitina, V. A., Nazmutdinov, R. R. & Tsirlina, G. A. Quinones electrochemistry in room-temperature ionic liquids. J. Phys. Chem. B 115, 668–677 (2011).
Oyama, M., Hoshino, T. & Okazaki, S. Solvent effect on the ion pair formation between 2,3,5,6-tetrachloro-1,4-benzoquinone anion radical and Mg2+ measured using a pulse electrolysis stopped flow method. J. Electroanal. Chem. 401, 243–246 (1996).
Hernández-Burgos, K., Rodríguez-Calero, G. G., Zhou, W., Burkhardt, S. E. & Abruña, H. D. Increasing the gravimetric energy density of organic based secondary battery cathodes using small radius cations (Li+ and Mg2+). J. Am. Chem. Soc. 135, 14532–14535 (2013).
Martin, R. P., Doub, W. H., Roberts, J. L. & Sawyer, D. T. Electrochemical reduction of sulfur in aprotic solvents. Inorg. Chem. 12, 1921–1925 (1973).
Lu, Y.-C., He, Q. & Gasteiger, H. A. Probing the lithium–sulfur redox reactions: a rotating-ring disk electrode study. J. Phys. Chem. C. 118, 5733–5741 (2014).
Huang, J.-Q. et al. Permselective graphene oxide membrane for highly stable and anti-self-discharge lithium–sulfur batteries. ACS Nano 9, 3002–3011 (2015).
Tian, J., Zhou, X., Wu, Q. & Li, C. Li-salt mediated Mg-rhodizonate batteries based on ultra-large cathode grains enabled by K-ion pillaring. Energy Storage Mater. 22, 218–227 (2019).
Salama, M. et al. On the feasibility of practical Mg–S batteries: practical limitations associated with metallic magnesium anodes. ACS Appl. Mater. Interfaces 10, 36910–36917 (2018).
Adams, B. D., Zheng, J., Ren, X., Xu, W. & Zhang, J.-G. Accurate determination of coulombic efficiency for lithium metal anodes and lithium metal batteries. Adv. Energy Mater. 8, 1702097 (2018).
Luo, J., Bi, Y., Zhang, L., Zhang, X. & Liu, T. L. A stable, non-corrosive perfluorinated pinacolatoborate Mg electrolyte for rechargeable Mg batteries. Angew. Chem. Int. Ed. Engl. 58, 6967–6971 (2019).
Wang, W. et al. Graphene oxide membranes with tunable permeability due to embedded carbon dots. Chem. Commun. 50, 13089–13092 (2014).
Bitenc, J., Vizintin, A., Grdadolnik, J. & Dominko, R. Tracking electrochemical reactions inside organic electrodes by operando IR spectroscopy. Energy Storage Mater. 21, 347–353 (2019).
Gueon, D., Ju, M.-Y. & Moon, J. H. Complete encapsulation of sulfur through interfacial energy control of sulfur solutions for high-performance Li−S batteries. Proc. Natl Acad. Sci. USA 117, 12686–12692 (2020).
Li, Z., Zhang, J. T., Chen, Y. M., Li, J. & Lou, X. W. Pie-like electrode design for high-energy density lithium–sulfur batteries. Nat. Commun. 6, 8850 (2015).
Pei, F. et al. Self-supporting sulfur cathodes enabled by two-dimensional carbon yolk-shell nanosheets for high-energy-density lithium-sulfur batteries. Nat. Commun. 8, 482 (2017).
Kang, N. et al. Cathode porosity is a missing key parameter to optimize lithium-sulfur battery energy density. Nat. Commun. 10, 4597 (2019).
Singh, N. et al. Achieving high cycling rates via in situ generation of active nanocomposite metal anodes. ACS Appl. Energy Mater. 1, 4651–4661 (2018).
Liang, Y. et al. Universal quinone electrodes for long cycle life aqueous rechargeable batteries. Nat. Mater. 16, 841–848 (2017).
Pan, B. et al. Polyanthraquinone-based organic cathode for high-performance rechargeable magnesium-ion batteries. Adv. Energy Mater. 6, 1600140 (2016).
Qiao, R. et al. High-efficiency in situ resonant inelastic X-ray scattering (iRIXS) endstation at the Advanced Light Source. Rev. Sci. Instrum. 88, 033106 (2017).
Harris, R. K., Becker, E. D., Cabral de Menezes, S. M., Goodfellow, R. & Granger, P. NMR nomenclature: nuclear spin properties and conventions for chemical shifts: IUPAC recommendations 2001. Solid State Nucl. Magn. Reson. 22, 458–483 (2002).
Acknowledgements
Y.Y. acknowledges the support of University of Houston. R.M. and O.T. acknowledge the funding provided from Toyota Motor Corporation. This research used resources of the Advanced Light Source, which is a DOE Office of Science User Facility under contract no. DE-AC02-05CH11231. We acknowledge K. Suto, Y. Kotani, F. Mizuno, T. Matsunaga and H. Aso from Toyota Motor Corporation and K. Takechi from Toyota Central R&D, N. Singh, T. A. Arthur, R. Sugiura, P. Fanson and T. Inoue at Toyota Research Institute of North America for support and discussion.
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H.D., O.T., Y.L., R.M. and Y.Y. conceived and designed the experiments. O.T. and R.M. synthesized the electrolytes. H.D. synthesized and fabricated organic electrodes. H.D., O.T. and Y.Z. performed electrochemical and materials characterizations. H.D. and Y.Z. prepared GO membranes. W.Y. and Z.L.-H. performed soft X-ray absorption spectroscopy measurements. H.D., O.T., Y.L., R.M. and Y.Y. wrote the manuscript. R.M. and Y.Y. supervised the project.
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R.M. is inventor on US Patent 9240613 and O.T. and R.M. are inventors on US Patents 9252458 and 20180151917, which are assigned to Toyota Motor Engineering & Manufacturing North America, Inc. Y.Y., H.D. and Y.L. are inventors on US Patent 63043240. O.T. and R.M. are employees of Toyota Research Institute of North America, the research division at Toyota Motor Engineering & Manufacturing North America (TEMA), Inc.
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Supplementary Methods, Tables 1–3, Figs. 1–14 and Notes.
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Dong, H., Tutusaus, O., Liang, Y. et al. High-power Mg batteries enabled by heterogeneous enolization redox chemistry and weakly coordinating electrolytes. Nat Energy 5, 1043–1050 (2020). https://doi.org/10.1038/s41560-020-00734-0
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DOI: https://doi.org/10.1038/s41560-020-00734-0
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